Azo dyes from 2, 6 dihalo 4 nitraniline



. hal NOQM ha] I Patented June'3, 1947 AZO DYES FROM 2,6 DIHALO 4 NITRANHJNE Friedrich Felix, Base], and Rudolf von Capeller,

Riehen, Switzerland, assignors to Society .of Chemical Industry in Basie, Basel, Switzerland,

a Swiss firm No Drawing. Application February 26, 1945,

The manufacture of tria e-dyestuffs dyeing grey tints has been described in various specifications. These are generally dyestuffs consisting of a starting component of thebenzene or naphthalene series, a middle component such as naphthylamine and 6- or 7-sulfonic acid thereof, a second middle component of this group and a final component of the naphthalene series, for ex.- ample an aminonaphthalene derivative, such as an aminohydroxynaphthalene" sulfonic acid. These dyestuffs yield dyeings which are characterized by a remarkable fastness to light. All these dyeings, however, have the serious disadvantage of being sensitive when boiled in alkaline media. This property renders their application diflicult for many purposes where prolonged boiling is necessary, for example when dyeing materialswhich can be dyed through only difllcultly.

According to the present invention polyazodyestuffs oi the aforementioned constitution are obtained by coupling diazotized disazo-dyestutls oi the general formula wherein hal stands for one of the halogens chlorine and bromine, one at and one 1/ each stand for a hydrogen atom and one :v'and one 1 each stand for a hydrogen atom or a sulfonic acid group, with a sulfonated aminonaphthalene derivative. These polyazo-dyestuflfs yield grey dyeings which are characterized by a surprising fastness to boiling. They correspond to the general formula I ma uoi-Qre N=N N=N-R hal V I I ll 1/ wherein hal stands for one of the halogens chlorine and bromine, one x and one 1; each stand for a hydrogen atom and one a: and oney each stand for a hydrogen atom or asulfonic acid group, and R stands for a sulfonated aminonaphthalene' component. As sultonated aminonaphthalene derivatives there can be usedcompounds such as e. g., 1-phenylaminonaphthalene-8-sulfonic,acid, 1- (4'-methyl) phenylaminonaphthalene-B-sulionic acid, 2-aminonaphthalene-fi-sulfonic acid,

Niagara, i I

6 Claims. (Cl. 260-169) Serial No. 579,902. In Switzerland March 15,

2 sulfonic acids of amino-hydroxynaphthalenes and N-derivatives thereof, especially 2-amino-5- hydroxynaphthalene-7-sulfonic acid and N-substitution products thereof, such as 2-amino-5-hydroxynaphthalene-'7-sulfonic acid itself, 2-phenylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-(4'-methoxy) -phenylamino 5 hydroxynaphthalene-l-sulfonic acid, 2- (4-hydroxy) -phenylamin0-5-hydroxynaphthalene 'l-sulfonic acid-3'- carboxylic acid, 2-benzoy1amino-5-hydroxynaphthalene-l-sulfonic acid, thesecondary condensation product of 1 mol. of cyanuric chloride, 1 mol. of 2-amino 5-hydroxynaphthalene 7 suli'onic acid and 1 mol. of 1-am1nobenzene-3-sulfonic acid, the ternary condensation product from 1 mol. of eyanuric chloride, 1 mol. of 2-amino-5- hydroxynaphthalene-l-siilfonic acid, 1 mol. of 1- aminobenzene-B-sulfonic acid and 1 mol. of aniline, 2-a.mino-8-hydroxynaphthalene-6-sulfonic acid, 2-acetylamino 8 hydroxynaphthalene-G- suifonic acid, 2-(4'-methyl or 4'-methoxy)- phenylamino-8-hydroxynaphthalene 6-sulfonic acid, 2-amino 8-hydroxynaphthalene-3:6-disu1- Ionic acid, 2-amino-5-hydroxynaphthalene-1:7-

disulfonic acid, 2-benzoylamino-8-hydroxy-naphthalene-G-sulfonic acid, 1-aminc-5-hydroxynaphr thalene 'lsulfonic acid, 1-pheny1amino-5-hyq droxynaphthaieheJ-sulfonic acid, the ternary condensation product of 1 mol. of cyanuric chloride, 1 mol. of 1-amino-8-hydroxynaphthalene- 3 :fi-disulionic acid and 2 mols. of aniline, and the like.

Finally, there can also be used amino-hydroxynaphthalene derivatives which couple twice in an alkaline medium, for example the urea of 2- amino-5-hydroxynaphthalene-7-sulfonic acid, or the 2z2 -dinaphthylamine-5:5'-dihydroxy-7:7'-' disulfonic acid.

In the above indicated amino-hydroxynaphthalene derivatives, provided that they are capable of coupling in an acidor alkaline medium and thus lead to different dyestufl. groups (whether coupling is determined by the amino group or by the hydroxy group), the final component can be used both in an acid and in an alkaline medium.

The following examples illustrate the invention,but are not to be regarded as limiting it in any way, the parts being by weight:

Example 1 20.7 parts of l-amino-2:6-dichloro-4-nitrobenzene are diazotized inusual manner with m'trosylsulfuric acid, poured onto ice and mixed with 30 partsof magnesium oxide. To this is added a 2,421,583 a 3 4 I neutral solution of 22.3 parts or l-aminonaphpheuylamino -naphthalene-8-hydroxy-7-sulfonic tnalene-I-sulionic acid. The formation of dyeacid and the like. When using 1-phenylamino-8- stuff is accelerated,advantageously by addition of sulfonic acid instead of 2-amino-5-hydroxynaph-' sodium acetate, the precipitated dyestufl is sucthalene-l-sulionic acid itis advantageous to protion-flltered, suspended in water, made alkaline duce the dyestufl' in an acetic acid medium and with sodium carbonate and, it necessary, salted not in aine'dium alkaline with sodium carbonate. out with sodium chloride and again suction- Instead of the 2-amino-5-hydroxynaphthaiene-'lfiltered. This monoazo-dyestufl is further disulfonic acid there is used with good result a azotized in usual manner and coupled with 1 condensation product of this acid, e. g. the teramino-naphthalene-l-sulionic acid in an acetic 1o nary condensation product of 1 mol. oi cyanuric acid medium. The disazo-dyestufl thus obtained chloride with 1 mol. of 2-amino-5-hydroxynaphis further diazotized and coupled with 2-aminothalene-l-sulfonic acid, 1 mol. of l-aminoben- 5-hydroxynaphthalene-7-su1fonic acid in a mezene-3-sulionic acid and 1 mol. of aniline. The dium alkaline with sodium carbonate. It is then dyestuii! so obtained has the formula 01 T 0H 12H NOQN: VN=N N=N N/ a O|H S0111 OIK filtered, washed with a solution of sodium chlo- In all instances very similar products are obride and dried. The dyestufi forms a dark grey tained ii the 1-amino-2:6-dichloro-4-nltrobenpowder dissolving in water to give a blue-grey zene is replaced by the corresponding quantity of coloration. It dyes cotton from an aqueous solul-amino-Zzfi-dibromo' or '1-amino-2-chloro-6- tion grey tints of good iastness to washing and to bromo-d-nitrobenzene.

light. The dyestui! corresponds to the formula These dyestuil's are worked up in usual manner 05 and dye cotton grey tints of good tastness to boil-- ing and to light. N0 N: N=N N=N 1 nos NH, Example 2 0,1 80,}; 52.4 parts of the secondary condensation prod t 01' 1 mol. of cyanuric chloride with 1 mol. of When replacing the l-aminonaphthalene-7-sulionic acid by l-aminonaphthalene-B-suIIonic anumhydmxynaphthalene mimic acid there is obtained a dyestufl of the general acid and 1 of aniline are dissolved m 500 parts of water and 20 parts oi sodium carbonate. I Into this solution which has been cooledwith ice 40 there is introduced the diazo compound obtained formula l NO NIN =N N=N from 67.5 parts of the disazo-dyestufl which is Boas NH itself obtained by coupling diazotized l-aminoc1 I 2:fi-dichloroi-nltrobenzene and l-aminonaphsou; SOaH thalene-7-sulfonic acid, diazotizingthe monoazowhich has very similar properties The c dyestufi and coupling with a second molecule merciai mixture consisting of l-aminonaphthaf m n phtha1ene-7-sultonic acid. The lene-6-sulfonic acid and l-aminonaphthalene-7- dyestuflj thus formed is. salted out with sodi m sulfonic aci'dcan therefore also be used. chloride. It corresponds to the formula Cl on NH C/ ('3Cl N N NOQN: N==N 1 som I ia- 3 sour I By working in analogous manner and using 2- and dyes cotton grey tints. phenyl-amino-5 hydroxynaphthaiene-l-sulionic 6 Example 3 acid instead of Z-amino-5-hydroxynaphthalene 0 sulfonic acid there is obtained a dyestufl! yielding I A dye-bath is prepared with 0.5 per cent. of dyeings of even better fastness to light. This corthe dyestufl of Example 1 from l-amino-ZzB-diresponds to the formula chloro-bnitrobenzene, 1 mol. of l-aminonaphc1 on 7 N0r-N=N- N=N N= o1 HO'S- NH SOrH OiH I Instead of 2-amino-5 hydroxynaphthalene-7- thalene-7-sulionic acid, 1 mol. of l-aminonaphsulfonic acid there can further be used l-aminothalene-l-sulfonic acid and 1 mol. of 2-phenyl- 5-hydroxynaphthalene-7-sulfonic acid, 2-ami-- amino-5-hydroxynaphthalene-7-su1fonic acid and no-8-hydroxynaphthalene-6-sulfonic acid, 2- 2 per cent. of sodium carbonate. The cotton is 2,421,553 I introduced at 60 0., the bath is heated to the 3. A dyestuif corresponding in the free form to boil, 30 per cent. of sodium sulfate are added the general formula after hour and boiling is continued for a furr /2 hour. The cotton is dyed grey tints, I i The dyeing remains unchanged on prolonged 6 Nb N=N N: N=N fi boiling. V

Example 4 l l ,1 y I A dye-bath is prepared with 0.5 per cent. of the dyestufl' of Example 1 from 1-amino-2z6-di- 1o Zfig'gg: 3223 figghi ggg ziggggggfiggg wherein one a: and one 1! each stand for a hydroacid and l-aminonaphthalene-G-sulfonic acid 1 gen atom and one and stand for mol of the some commercial mixture and 1 mol member the group consisting of hydrogen and of 2-pheny1amino-5-hydroxynaphthalene-7-su1- fig i zgg i gg ig summated ammo Ionic acid and 2 per cent. of sodium carbonate. 15 4 A dyestufl, c

a orresponding in the free form to V1scose rayon isnintroduced at 60 0., the bath the general formula is heated to 90-95 (3., 30 per. cent. of sodium sulfate are added and boiling is continued for a furthery hour. The viscose rayon is dyed grey n81 tints. The dyeing remains unchanged on proso N =N .N= N=1- I-R longed boiling. 7

What we claim is: 7 m 1. A dyestufl' corresponding in thefree form l t r z I I to the general formula 25 wherein hal stands for one of the halogens chlorine and bromine, one x and one 1 each N0 stand for a hydrogen atom and one a: and one u eachstand for a member of the group consisting a! so of hydrogen and SOuH, and It stands for a N- g phenylated 5 lwdroxy-2-aminonaphthalene-7- I Z U V sulfonic acid compound.

wherein hal stands for one of the halogens chio- 5. The dyestufl' of thei'ormuia 01 v I on 3 1 nois 402G I our on Y rine and bromine, one a: and one 1/ each stand 6 The dyestufi of the formula for a hydrogen atom and one a: and one 1! each 1 0 stand for a member of the group consisting of c H hydrogen and 803K, and R stands for a sulfonated N N= N=N N=N aminonaphthalene compound. 5 Ho 2. A dyestuff corresponding in the free form 1 I on 7 our to the general formula mmnnrcn mm RUDOLF v.01: csrmm so N0 N= N=N ran-n REFERENCES CITED I The following references are of record in the v flle of patent: I r w 1 55 'um'rrm sum ram-rs i Number Name 1 Date wherein hal stands for one of the halogens chlo- 1,270,290 Hagemann- June 25, 1918 rine and bromine, one a: and one 1: each stand for a hydrogen atom and one a: and one 1! each 3 I FOREIGN PAW stand for a member of the group consisting of 60 Number Country Date hydrogen and 801K, and R stands for a 81l1- 852,042 France Oct. 18, 1939 fonated hydroxyaminonaphthalene compound. 118,157 Switzerland Dec. 16, 1926 

